WO2009125721A1 - Composé chimique utilisé pour un transistor organique en couches minces et transistor organique en couches minces - Google Patents

Composé chimique utilisé pour un transistor organique en couches minces et transistor organique en couches minces Download PDF

Info

Publication number
WO2009125721A1
WO2009125721A1 PCT/JP2009/056933 JP2009056933W WO2009125721A1 WO 2009125721 A1 WO2009125721 A1 WO 2009125721A1 JP 2009056933 W JP2009056933 W JP 2009056933W WO 2009125721 A1 WO2009125721 A1 WO 2009125721A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
organic thin
thin film
film transistor
Prior art date
Application number
PCT/JP2009/056933
Other languages
English (en)
Japanese (ja)
Inventor
裕基 中野
雅俊 齊藤
浩昭 中村
Original Assignee
出光興産株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 出光興産株式会社 filed Critical 出光興産株式会社
Priority to JP2010507225A priority Critical patent/JP5452476B2/ja
Publication of WO2009125721A1 publication Critical patent/WO2009125721A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
    • C07C15/50—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals polycyclic non-condensed
    • C07C15/54—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals polycyclic non-condensed containing a group with formula
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
    • C07C15/56—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals polycyclic condensed
    • C07C15/58—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals polycyclic condensed containing two rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
    • C07C15/56—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals polycyclic condensed
    • C07C15/60—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals polycyclic condensed containing three rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
    • C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
    • C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
    • C07C22/08—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/24—Anthracenes; Hydrogenated anthracenes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate

Definitions

  • the present invention relates to a compound for an organic thin film transistor and an organic thin film transistor using the compound for an organic semiconductor layer.
  • Thin film transistors are widely used as display switching elements for liquid crystal display devices and the like.
  • a cross-sectional structure of a typical TFT is shown in FIG.
  • a typical TFT has a gate electrode, an insulator layer, and an organic semiconductor layer in this order on a substrate, a source electrode formed on the organic semiconductor layer at a predetermined interval, and It has a drain electrode.
  • the organic semiconductor layer forms a channel region, and an on / off operation is performed by controlling a current flowing between the source electrode and the drain electrode with a voltage applied to the gate electrode.
  • this TFT has been manufactured using amorphous or polycrystalline silicon.
  • a CVD apparatus used for manufacturing such a TFT using silicon is very expensive, and a display device using the TFT.
  • Such an increase in size has a problem in that it involves a significant increase in manufacturing costs.
  • the process of forming amorphous or polycrystalline silicon is performed at a very high temperature, the types of materials that can be used as a substrate are limited, and thus there is a problem that a lightweight resin substrate cannot be used. there were.
  • a TFT using an organic substance instead of amorphous or polycrystalline silicon (hereinafter sometimes abbreviated as an organic TFT) has been proposed.
  • Vacuum deposition and coating methods are known as film formation methods used when forming TFTs with organic materials.
  • film formation methods it is possible to increase the size of the element while suppressing an increase in manufacturing cost.
  • the process temperature required for film formation can be made relatively low.
  • the organic TFT has an advantage that there are few restrictions when selecting a material to be used for the substrate, and its practical use is expected, and research reports have been actively made.
  • materials for p-type FETs include polymers such as conjugated polymers and thiophenes, metal phthalocyanine compounds, condensed aromatic hydrocarbons such as pentacene, etc. Used in the form of a mixture with a compound.
  • Examples of the material of the n-type FET include 1,4,5,8-naphthalenetetracarboxyldianhydride (NTCDA), 11,11,12,12-tetracyanonaphtho-2,6-quinodimethane (TCNNQD). 1,4,5,8-naphthalenetetracarboxyldiimide (NTCDI) and fluorinated phthalocyanine are known.
  • an organic electroluminescence (EL) element as a device that similarly uses electric conduction.
  • a strong electric field of 10 5 V / cm or more is generally applied in the film thickness direction of an ultrathin film of 100 nm or less, whereas in the case of an organic TFT, a charge of several ⁇ m or more is applied. It is necessary to flow charges at a high speed with an electric field of a distance of 10 5 V / cm or less, and the organic substance itself needs further conductivity.
  • the above-described compound in the conventional organic TFT has a small field effect mobility, a slow response speed, and a problem in high-speed response as a transistor. Also, the on / off ratio was small.
  • the on / off ratio here refers to the current flowing between the source and drain when the gate voltage is applied (on) divided by the current flowing between the source and drain when the gate voltage is not applied (off).
  • the on-current is a current value (saturation current) when the current flowing between the source and the drain is normally saturated while increasing the gate voltage.
  • Patent Document 1 discloses that when bisacetylenyl acetylene is used as a transistor material, high mobility is exhibited.
  • naphthalene, anthracene and tetracene substituted with halogen atoms which are used as raw materials for synthesizing the compounds shown in this document, have a disadvantage that they are more expensive than benzene substituted with halogen atoms.
  • the present invention has been made to solve the above-mentioned problems, and since raw materials are readily available and can be synthesized by a general synthesis method, a compound for an organic thin film transistor having a low production cost, and An object of the present invention is to provide an organic thin film transistor having a high response speed (driving speed) when used as an organic semiconductor layer.
  • the present inventors have obtained a compound for an organic thin film transistor represented by the following formula (1) that can be synthesized simply and inexpensively in the organic semiconductor layer of the organic thin film transistor. It has been found that the response speed (driving speed) can be increased by using it, and the present invention has been completed.
  • this invention is a compound for organic thin-film transistors which has a structure of following formula (1).
  • X is represented by any one of the following three structures of the formulas (2) to (4).
  • Ar 1 is an aromatic hydrocarbon group having 6 to 60 carbon atoms, an aromatic heterocyclic group having 1 to 60 carbon atoms, or a group having a structure in which two or more of these aromatic groups are linked.
  • the group may have a substituent.
  • R 1 to R 5 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an alkyl group having 1 to 30 carbon atoms.
  • a ring structure including a nitrogen atom may be formed), an alkylsulfonyl group having 1 to 30 carbon atoms, a haloalkylsulfonyl group having 1 to 30 carbon atoms; an aromatic hydrocarbon group having 6 to 60 carbon atoms, and 3 to 3 carbon atoms
  • each of these groups may have a substituent.
  • each of R 6 to R 15 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an alkyl group having 1 to 30 carbon atoms.
  • a ring structure containing a nitrogen atom may be formed), an alkylsulfonyl group having 1 to 30 carbon atoms, a haloalkylsulfonyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, and 3 to 3 carbon atoms
  • An aromatic heterocyclic group having 60 carbon atoms, an alkylsilyl group having 3 to 20 carbon atoms which may have a substituent, an alkylsilylacetylene group having 5 to 60 carbon atoms or a cyano group, each of these groups having a substituent Or an adjacent group may be connected to each other to form an aromatic hydro
  • the present invention provides an organic substrate in which at least three terminals of a gate electrode, a source electrode and a drain electrode, an insulator layer, and an organic semiconductor layer are provided on a substrate, and a source-drain current is controlled by applying a voltage to the gate electrode.
  • the organic semiconductor layer provides an organic thin film transistor containing an organic compound having the structure of the formula (1).
  • the present invention also provides an organic thin film light emitting transistor that emits light by using a current flowing between a source and a drain in an organic thin film transistor and controls light emission by applying a voltage to a gate electrode.
  • the organic thin film transistor compound according to the present invention can be synthesized at a low manufacturing cost because the raw materials are easily available and can be synthesized by a general synthesis method.
  • this compound is used as an organic semiconductor layer, an organic thin film transistor having a high response speed (driving speed) can be provided.
  • FIG. 1 It is a figure which shows an example of the element structure of the organic thin-film transistor of this invention. It is a figure which shows an example of the element structure of the organic thin-film transistor of this invention. It is a figure which shows an example of the element structure of the organic thin-film transistor of this invention. It is a figure which shows an example of the element structure of the organic thin-film transistor of this invention. It is a figure which shows an example of the element structure of the organic thin-film transistor of this invention. It is a figure which shows an example of the element structure of the organic thin-film transistor of this invention. It is a figure which shows an example of the element structure of the organic thin-film transistor in the Example of this invention. It is a figure which shows the manufacturing process of the source electrode and drain electrode provided with the positive hole injection property electrode and the electron transport property electrode. It is a figure which shows the emission spectrum of the organic thin film light emitting transistor of this invention obtained in Example 6.
  • FIG. 1 shows the manufacturing process of the source electrode and drain electrode provided with the positive hole injection
  • the compound for an organic thin film transistor of the present invention has a structure represented by the following formula (1).
  • Ar 1 is an aromatic hydrocarbon group having 6 to 60 carbon atoms, an aromatic heterocyclic group having 1 to 60 carbon atoms, or a structure in which two or more of these aromatic groups are linked, Each group may have a substituent.
  • Ar 1 is preferably a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms.
  • Ar 1 is preferably a substituted or unsubstituted aromatic heterocyclic group having 1 to 60 carbon atoms.
  • aromatic hydrocarbon group for Ar 1 examples include optionally substituted benzene, naphthalene, anthracene, tetracene, pentacene, phenanthrene, chrysene, triphenylene, corannulene, coronene, hexabenzotriphenylene, hexabenzocoronene. And residues such as sumanen.
  • aromatic heterocyclic group for Ar 1 examples include pyridine, pyrazine, quinoline, naphthyridine, quinoxaline, phenazine, diazaanthracene, pyridoquinoline, pyrimidoquinazoline, pyrazinoquinoxaline, phenanthroline, which may have a substituent.
  • the structure in which two or more aromatic groups of Ar 1 are connected is a combination of the specific examples of the aromatic hydrocarbon group and aromatic heterocyclic group, and specific examples include biphenylene, terphenylene, and binaphthalene. , Bianthracene, phenylthiophene, thienylnaphthalene, thienylanthracene, phenylnaphthalene, phenylanthracene, pyridylnaphthalene, pyridylanthracene, bithiophene, terthiophene and the like.
  • Ar 1 may have a substituent, benzene, naphthalene, anthracene, tetracene, pentacene, phenanthrene, chrysene, pyridine, pyrazine, quinoline, naphthyridine, quinoxaline, phenazine, diazaanthracene, pyridoquinoline , Pyrimidoquinazoline, pyrazinoquinoxaline, phenanthroline, carbazole, dibenzothiophene, thienothiophene, dithienothiophene, [1] benzothieno [3,2-b] benzothiophene, biphenylene, terphenylene, binaphthalene, bianthracene, phenylthiophene, From thienylnaphthalene, thienylanthracene, phenylnaphthalene, phenylanthracene, phen
  • Examples of the substituent for Ar 1 include an aromatic hydrocarbon group, an aromatic heterocyclic group, an alkyl group, an alkoxy group, an aryloxy group, an arylthio group, an alkoxycarbonyl group, an amino group, a halogen atom, a cyano group, a nitro group, A hydroxyl group, a carboxyl group, etc. are mentioned.
  • X is represented by any of the structures of the following formulas (2) to (4).
  • R 1 to R 5 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms.
  • Alkyl groups may be bonded to each other to form a ring structure containing a nitrogen atom
  • R 6 to R 15 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or a carbon number.
  • an aromatic hydrocarbon group having 6 to 60 carbon atoms, an aromatic heterocyclic group having 3 to 60 carbon atoms, or carbon atoms 6 to 60 saturated cyclic structures may be formed.
  • R 1 to R 15 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkylsilylacetylene group having 5 to 60 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, or A cyano group is preferred.
  • At least two adjacent groups in R 6 to R 15 are connected to each other to form an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic complex having 3 to 60 carbon atoms.
  • a ring group is preferably formed.
  • the organic thin film transistor compound of the present invention is basically bipolar showing p-type (hole conduction) and n-type (electron conduction), and can be used as a p-type element in combination with the source and drain electrodes described later.
  • Preferred as the electron-accepting group are a hydrogen atom, a halogen atom, a cyano group, a haloalkyl group having 1 to 30 carbon atoms, a haloalkoxy group having 1 to 30 carbon atoms, and a haloalkylsulfonyl group having 1 to 30 carbon atoms.
  • an electron donating group as a substituent on R 1 to R 15 and Ar 1 , the highest occupied orbital (HOMO) level can be increased and the p-type semiconductor can function.
  • Preferred examples of the electron donating group include a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, and a dialkylamino group having 2 to 60 carbon atoms.
  • the amino groups may be bonded to each other to form a ring structure containing a nitrogen atom).
  • halogen atom examples include fluorine, chlorine, bromine and iodine atoms.
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, and n-heptyl group.
  • N-octyl group N-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group N-octadecyl group, n-nonadecyl group, n-icosane group, n-henicosane group, n-docosane group, n-tricosane group, n-tetracosane group, n-pentacosane group, n-hexacosane group, n-heptacosane group N-octacosane group, n-nonacosane group, n-triacontan
  • haloalkyl group examples include chloromethyl group, 1-chloroethyl group, 2-chloroethyl group, 2-chloroisobutyl group, 1,2-dichloroethyl group, 1,3-dichloroisopropyl group, 2,3-dichloro- t-butyl group, 1,2,3-trichloropropyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group, 1,2-dibromoethyl group, 1,3-dibromoisopropyl group, 2,3-dibromo-t-butyl group, 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group, 1, 3-diio
  • the alkoxy group is a group represented by —OX 1
  • examples of X 1 include the same examples as described for the alkyl group
  • the haloalkoxy group is represented by —OX 2.
  • examples of X 2 include the same examples as described for the haloalkyl group.
  • the alkylthio group is a group represented by —SX 1 and examples of X 1 include the same examples as described for the alkyl group.
  • the haloalkylthio group is represented by —SX 2 Examples of X 2 include the same examples as described for the haloalkyl group.
  • the alkylamino group is a group represented by —NHX 1 ; the dialkylamino group is a group represented by —NX 1 X 3 ; and X 1 and X 3 are the same as those described for the alkyl group, respectively. Similar examples are given.
  • the alkyl group of the dialkylamino group may be bonded to each other to form a ring structure containing a nitrogen atom. Examples of the ring structure include pyrrolidine and piperidine.
  • the alkylsulfonyl group is a group represented by —SO 2 X 1 , and examples of X 1 include the same examples as described for the alkyl group, and the haloalkylsulfonyl group includes —SO 2 a group represented by X 2, examples of X 2 are examples similar to those described in the haloalkyl group.
  • aromatic hydrocarbon group examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a perylenyl group, a tetracenyl group, and a pentacenyl group.
  • aromatic heterocyclic group examples include a dithienophenyl group, a benzofuranyl group, a benzothiophenyl group, a quinolinyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, and a benzothiadiazonyl group.
  • the alkylsilyl group is a group represented by —SiX 1 X 3 X 4 , and examples of X 1 , X 3 and X 4 are the same as those described for the alkyl group.
  • the alkylsilylacetylene group is a group in which a group represented by the alkylsilyl group is interposed via an ethynylene group, and examples thereof include a trimethylsilylacetylene group, a triethylsilylacetylene group, and a triisopropylsilylacetylene group.
  • examples of the group having a structure in which two or more aromatic hydrocarbon groups having 6 to 60 carbon atoms and / or aromatic heterocyclic groups having 3 to 60 carbon atoms are linked include Ar 1 described above. The same thing is mentioned. As the aromatic hydrocarbon group or aromatic heterocyclic group formed by connecting adjacent groups among R 6 to R 15 , the aromatic hydrocarbon group and aromatic heterocyclic group described above are explained. Examples similar to the above are given.
  • saturated cyclic structure examples include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a 1,4-dioxanyl group.
  • Examples of the substituent for R 1 to R 15 include an aromatic hydrocarbon group, an aromatic heterocyclic group, an alkyl group, an alkoxy group, an aryloxy group, an arylthio group, an alkoxycarbonyl group, an amino group, a halogen atom, a cyano group, A nitro group, a hydroxyl group, a carboxyl group, etc. are mentioned.
  • the compound for an organic thin film transistor of the present invention can be synthesized by a known method, for example, a coupling reaction using a transition metal catalyst represented by a Sonogashira coupling reaction as shown below.
  • an electronic device such as a transistor
  • a device with high field-effect mobility and a high on / off ratio can be obtained by using a material with high purity. Therefore, it is desirable to add purification by techniques such as column chromatography, recrystallization, distillation, sublimation, etc. as necessary. Preferably, it is possible to improve the purity by repeatedly using these purification methods or combining a plurality of methods. Furthermore, it is desirable to repeat sublimation purification at least twice as a final step of purification. By using these methods, it is preferable to use a material having a purity of 90% or more measured by HPLC, more preferably 95% or more, and particularly preferably 99% or more. In addition, the on / off ratio can be increased and the performance inherent to the material can be extracted.
  • the device configuration of the organic thin film transistor of the present invention has at least three terminals of a gate electrode, a source electrode and a drain electrode, an insulator layer, and an organic semiconductor layer, and a source-drain current is controlled by applying a voltage to the gate electrode.
  • an organic-semiconductor layer contains the compound for organic thin-film transistors of this invention mentioned above, It is characterized by the above-mentioned.
  • an organic thin film transistor is provided on a substrate.
  • the structure of the transistor is not particularly limited, and components other than the components of the organic semiconductor layer may have a known element configuration. A specific example of the element configuration of the organic thin film transistor will be described with reference to the drawings.
  • the organic thin film transistor 1 of FIG. 1 has a source electrode 11 and a drain electrode 12 formed on a substrate 10 so as to face each other with a predetermined interval. And the organic-semiconductor layer 13 is formed so that the source electrode 11, the drain electrode 12, and the gap
  • a gate electrode 15 is formed on the insulator layer 14 and on the gap between the source electrode 11 and the drain electrode 12.
  • the organic thin film transistor 2 in FIG. 2 has a gate electrode 15 and an insulator layer 14 in this order on a substrate 10, and a pair of source electrode 11 and drain formed on the insulator layer 14 with a predetermined interval therebetween.
  • An electrode 12 is provided, and an organic semiconductor layer 13 is formed thereon.
  • the organic thin film transistor 3 in FIG. 3 has a gate electrode 15, an insulator layer 14, and an organic semiconductor layer 13 in this order on a substrate 10.
  • a source electrode 11 and a drain electrode 12 are provided.
  • the insulating layer 14 and the gate electrode 15 are provided in this order.
  • the organic thin film transistor of the present invention has a field effect transistor (FET: Field Effect Transistor) structure. As described above, there are several configurations depending on the position of the electrodes, the layer stacking order, and the like.
  • the organic thin film transistor is formed with an organic semiconductor layer (organic compound layer), a source electrode and a drain electrode formed to face each other with a predetermined distance, and a predetermined distance from the source electrode and the drain electrode. And a current flowing between the source and drain electrodes is controlled by applying a voltage to the gate electrode.
  • the distance between the source electrode and the drain electrode is determined by the use of the organic thin film transistor of the present invention, and is usually 0.1 ⁇ m to 1 mm, preferably 1 ⁇ m to 100 ⁇ m, and more preferably 5 ⁇ m to 100 ⁇ m.
  • the organic thin film transistor of the present invention is turned on / off, amplified, etc. by controlling the current flowing between the source electrode and the drain electrode by the voltage applied to the gate electrode. If it is a mechanism in which the effect of this is expressed, it is not limited to these element structures.
  • the top-and-bottom contact organic thin-film transistor proposed by Yoshida et al. Of the National Institute of Advanced Industrial Science and Technology in the 49th Conference on Applied Physics Related Lectures 27a-M-3 (March 2002) (see Fig. 5)
  • a vertical organic thin-film transistor proposed by Kudo et al. Of Chiba University in IEEJ Transactions 118-A (1998), 1440.
  • the constituent members of the organic thin film transistor will be described.
  • the organic-semiconductor layer in the organic thin-film transistor of this invention contains the compound for organic thin-film transistors of this invention mentioned above.
  • the thickness of the organic semiconductor layer is not particularly limited, but is usually 0.5 nm to 1 ⁇ m, preferably 2 nm to 250 nm.
  • a method for forming the organic semiconductor layer is not particularly limited, and a known method can be applied.
  • MBE molecular beam deposition
  • vacuum deposition chemical deposition
  • chemical deposition dipping of a solution in which a material is dissolved in a solvent
  • the organic semiconductor layer is made of the material.
  • the crystallinity of the organic semiconductor layer is improved, the field effect mobility is improved. Therefore, when film formation from a gas phase (evaporation, sputtering, etc.) is used, it is desirable to maintain the substrate temperature during film formation at a high temperature.
  • the temperature is preferably 50 to 250 ° C., more preferably 70 to 150 ° C.
  • the annealing temperature is preferably 50 to 200 ° C., more preferably 70 to 200 ° C., and the time is preferably 10 minutes to 12 hours, more preferably 1 to 10 hours.
  • one kind of material may be used for the organic semiconductor layer, and a plurality of thin films mixed with a plurality of materials or a plurality of different materials made of known semiconductors such as pentacene and thiophene oligomers may be used. These layers may be laminated.
  • the substrate in the organic thin film transistor of the present invention plays a role of supporting the structure of the organic thin film transistor.
  • a material in addition to glass, inorganic compounds such as metal oxides and nitrides, plastic films (PET, PES, PC) It is also possible to use metal substrates or composites or laminates thereof.
  • PET, PES, PC plastic films
  • metal substrates or composites or laminates thereof when the structure of the organic thin film transistor can be sufficiently supported by the components other than the substrate, it is possible not to use the substrate.
  • a silicon (Si) wafer is often used as a material for the substrate.
  • Si itself can be used as a gate electrode / substrate.
  • the surface of Si can be oxidized to form SiO 2 and used as an insulating layer.
  • a metal layer such as Au may be formed on the Si substrate serving as the substrate and gate electrode as an electrode for connecting the lead wire.
  • the material for the gate electrode, the source electrode, and the drain electrode is not particularly limited as long as it is a conductive material.
  • Examples of the method for forming the electrode include means such as vapor deposition, electron beam vapor deposition, sputtering, atmospheric pressure plasma method, ion plating, chemical vapor deposition, electrodeposition, electroless plating, spin coating, printing, and ink jet. It is done.
  • a conductive thin film formed using the above method is formed using a known photolithographic method or a lift-off method, on a metal foil such as aluminum or copper.
  • a resist is formed and etched by thermal transfer, ink jet, or the like.
  • the thickness of the electrode formed in this way is not particularly limited as long as current is conducted, but is preferably in the range of 0.2 nm to 10 ⁇ m, more preferably 4 nm to 300 nm. If it is in this preferable range, the resistance is increased due to the thin film thickness, and a voltage drop does not occur. In addition, since the film is not too thick, it does not take time to form the film, and when another layer such as a protective layer or an organic semiconductor layer is laminated, the laminated film can be smooth without causing a step.
  • a source electrode, a drain electrode, a gate electrode and a method for forming the source electrode are formed using a fluid electrode material containing the above conductive material, such as a solution, paste, ink, or dispersion.
  • a fluid electrode material containing a conductive polymer or metal fine particles containing platinum, gold, silver, or copper is preferable.
  • the solvent or dispersion medium is preferably a solvent or dispersion medium containing 60% by mass or more, preferably 90% by mass or more of water, in order to suppress damage to the organic semiconductor.
  • the dispersion containing metal fine particles for example, a known conductive paste or the like may be used, but a dispersion containing metal fine particles having a particle size of usually 0.5 nm to 50 nm, 1 nm to 10 nm is preferable.
  • the material of the fine metal particles include platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, and tungsten. Zinc or the like can be used.
  • an electrode using a dispersion in which these metal fine particles are dispersed in water or a dispersion medium which is an arbitrary organic solvent using a dispersion stabilizer mainly composed of an organic material.
  • a method for producing such a dispersion of metal fine particles metal ions can be reduced in the liquid phase, such as a physical generation method such as gas evaporation method, sputtering method, metal vapor synthesis method, colloid method, coprecipitation method, etc.
  • a chemical production method for producing metal fine particles preferably disclosed in JP-A-11-76800, JP-A-11-80647, JP-A-11-319538, JP-A-2000-239853, and the like.
  • metal fine particle dispersions may be directly patterned by an ink jet method, or may be formed from a coating film by lithograph or laser ablation. Moreover, the patterning method by printing methods, such as a letterpress, an intaglio, a lithographic plate, and screen printing, can also be used. After the electrode is formed and the solvent is dried, the metal fine particles are heat-fused by heating in a shape within a range of 100 ° C. to 300 ° C., preferably 150 ° C. to 200 ° C., if necessary. An electrode pattern having the following shape is formed.
  • a known conductive polymer whose conductivity is improved by doping is also preferable to use as a material for the gate electrode, the source electrode, and the drain electrode.
  • a known conductive polymer whose conductivity is improved by doping for example, conductive polyaniline, conductive polypyrrole, conductive polythiophene (polyethylene diene). Oxythiophene and polystyrene sulfonic acid complexes, etc.), polyethylene dioxythiophene (PEDOT) and polystyrene sulfonic acid complexes, and the like are also preferably used. These materials can reduce the contact resistance between the organic semiconductor layer of the source electrode and the drain electrode.
  • These forming methods may also be patterned by an ink jet method, or may be formed from a coating film by lithography, laser ablation, or the like.
  • the patterning method by printing methods such as a letterpress, an intaglio, a lithographic plate, and screen printing, can also be used.
  • the material for forming the source electrode and the drain electrode is preferably a material having a small electric resistance at the contact surface with the organic semiconductor layer among the examples described above.
  • the electrical resistance at this time corresponds to the field-effect mobility when the current control device is manufactured, and it is necessary that the resistance be as small as possible in order to obtain a large mobility.
  • This is generally determined by the magnitude relationship between the work function of the electrode material and the energy level of the organic semiconductor layer.
  • the work function (W) of the electrode material is a
  • the ionization potential of the organic semiconductor layer is (Ip) b
  • the electron affinity (Af) of the organic semiconductor layer is c
  • a, b, and c are all positive values based on the vacuum level.
  • ba ⁇ 1.5 eV (formula (I)) is preferable, and ba ⁇ 1.0 eV is more preferable. If the above relationship can be maintained in relation to the organic semiconductor layer, a high-performance device can be obtained.
  • the electrode material has a work function as large as possible, and the work function is 4.0 eV or more.
  • the work function is preferably 4.2 eV or more.
  • the value of the work function of a metal is, for example, an effective metal having a work function of 4.0 eV or higher as described in Chemistry Handbook Fundamentals II-493 (revised 3 edition, published by The Chemical Society of Japan, Maruzen 1983)
  • the high work function metal is mainly Ag (4.26, 4.52, 4.64, 4.74 eV), Al (4.06, 4.24, 4.41 eV), Au (5.1, 5.37, 5.47 eV), Be (4.98 eV), Bi (4.34 eV), Cd (4.08 eV), Co (5.0 eV), Cu (4.65 eV), Fe (4.5, 4.67, 4.81 eV), Ga (4.3 eV), Hg (4.4 eV), Ir (5.42, 5.76 eV), Mn (4.1 eV), Mo (4 .53, 4.55, 4.95 eV), Nb (4.02, 4.3) , 4.87 eV), Ni (5.04, 5.22, 5.35 eV), Os (5.93
  • the work function of the electrode material is preferably as small as possible, and the work function is preferably 4.3 eV or less. More preferably, the work function is 3.7 eV or less.
  • the low work function metal it has a work function of 4.3 eV or less as described in, for example, Chemical Handbook, Basics, pages II-493 (revised 3rd edition, published by The Chemical Society of Japan, Maruzen Co., Ltd.
  • the electrode material contains one or more of these low work function substances, there is no particular limitation as long as the work function satisfies the above formula (II).
  • the low work function metal easily deteriorates when exposed to moisture and oxygen in the atmosphere, it is desirable to coat with a stable metal in the air such as Ag or Au as necessary.
  • the film thickness necessary for the coating is 10 nm or more, and as the film thickness increases, the film can be protected from oxygen and water. However, for practical reasons, the thickness is preferably 1 ⁇ m or less for the purpose of increasing productivity.
  • a buffer layer may be provided between the organic semiconductor layer and the source and drain electrodes for the purpose of improving the injection efficiency.
  • the buffer layer has an alkali metal or alkaline earth metal ion bond such as LiF, Li 2 O, CsF, NaCO 3 , KCl, MgF 2 , and CaCO 3 used for an organic EL cathode for an n-type organic thin film transistor.
  • Alq alkali metal or alkaline earth metal ion bond
  • cyano compounds such as FeCl 3 , TCNQ, F 4 -TCNQ, HAT, CFx, GeO 2 , SiO 2 , MoO 3 , V 2 O 5 , VO 2 , V 2 O 3 , MnO, Metal oxides other than alkali metals and alkaline earth metals such as Mn 3 O 4 , ZrO 2 , WO 3 , TiO 2 , In 2 O 3 , ZnO, NiO, HfO 2 , Ta 2 O 5 , ReO 3 , PbO 2 Inorganic compounds such as ZnS and ZnSe are desirable. In many cases, these oxides cause oxygen vacancies, which are suitable for hole injection. Further, amine compounds such as TPD and NPD, and compounds used as a hole injection layer and a hole transport layer in an organic EL device such as CuPc may be used. Moreover, what consists of two or more types of said compounds is desirable.
  • the buffer layer has the effect of lowering the threshold voltage by lowering the carrier injection barrier and driving the transistor at a low voltage
  • the buffer layer only needs to be thin between the electrode and the organic semiconductor layer, and the thickness is 0.1 nm to 30 nm, preferably 0.3 nm to 20 nm.
  • the material of the insulator layer in the organic thin film transistor of the present invention is not particularly limited as long as it has electrical insulation and can be formed as a thin film.
  • Metal oxide including silicon oxide
  • metal nitride (Including silicon nitride)
  • polymers low molecular organic molecules, and the like, materials having an electrical resistivity at room temperature of 10 ⁇ cm or more can be used, and an inorganic oxide film having a high relative dielectric constant is particularly preferable.
  • Inorganic oxides include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate, lead lanthanum titanate, strontium titanate, Barium titanate, barium magnesium fluoride, lanthanum oxide, fluorine oxide, magnesium oxide, bismuth oxide, bismuth titanate, niobium oxide, strontium bismuth titanate, strontium bismuth tantalate, tantalum pentoxide, niobium tantalate Examples thereof include bismuth acid, trioxide yttrium, and combinations thereof, and silicon oxide, aluminum oxide, tantalum oxide, and titanium oxide are preferable.
  • inorganic nitrides such as silicon nitride (Si 3 N 4 , SixNy (x, y> 0)) and aluminum nitride can be suitably used.
  • the insulator layer may be formed of a precursor containing an alkoxide metal, and the insulator layer is formed by coating a solution of the precursor on a substrate, for example, and subjecting it to a chemical solution treatment including heat treatment. It is formed.
  • the metal in the alkoxide metal is selected from, for example, a transition metal, a lanthanoid, or a main group element.
  • alkoxide in the alkoxide metal examples include, for example, alcohols including methanol, ethanol, propanol, isopropanol, butanol, isobutanol, methoxyethanol, ethoxyethanol, propoxyethanol, butoxyethanol, pentoxyethanol, heptoxyethanol, Examples thereof include those derived from alkoxy alcohols including methoxypropanol, ethoxypropanol, propoxypropanol, butoxypropanol, pentoxypropanol, heptoxypropanol, and the like.
  • the insulator layer when the insulator layer is made of the above-described material, polarization easily occurs in the insulator layer, and the threshold voltage for transistor operation can be reduced. Further, among the above materials, in particular, when an insulator layer is formed of silicon nitride such as Si 3 N 4 , SixNy, or SiONx (x, y> 0), a depletion layer is more easily generated, and the threshold of transistor operation is increased. The voltage can be further reduced.
  • polyimide, polyamide, polyester, polyacrylate, photo radical polymerization system, photo cation polymerization system photo-curable resin, copolymer containing acrylonitrile component, polyvinyl phenol, polyvinyl alcohol, A novolac resin, cyanoethyl pullulan, or the like can also be used.
  • a material having water repellency is particularly preferable.
  • the interaction between the insulator layer and the organic semiconductor layer can be suppressed, and the crystallinity of the organic semiconductor layer can be improved by utilizing the cohesiveness inherent in the organic semiconductor, thereby improving the device performance.
  • Examples of this include Yasuda et al. Jpn. J. et al. Appl. Phys. Vol. 42 (2003) p.
  • the polyparaxylylene derivatives described in 6614-6618 and Janos Veres et al. Chem. Mater. , Vol. 16 (2004) p. 4543-4555 can be mentioned.
  • the organic semiconductor layer can be formed with less damage. Therefore, it is an effective method.
  • the insulator layer may be a mixed layer using a plurality of inorganic or organic compound materials as described above, or may be a laminated structure of these. In this case, the performance of the device can be controlled by mixing or laminating a material having a high dielectric constant and a material having water repellency, if necessary.
  • the insulator layer may include an anodic oxide film or the anodic oxide film as a configuration.
  • the anodized film is preferably sealed.
  • the anodized film is formed by anodizing a metal that can be anodized by a known method. Examples of the metal that can be anodized include aluminum and tantalum, and the anodizing method is not particularly limited, and a known method can be used.
  • An oxide film is formed by anodizing. Any electrolyte solution that can form a porous oxide film can be used as the anodizing treatment. Generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, boric acid, sulfamic acid, benzenesulfone, and the like can be used. An acid or the like or a mixed acid obtained by combining two or more of these or a salt thereof is used.
  • the treatment conditions for anodization vary depending on the electrolyte used and cannot be specified in general. In general, however, the concentration of the electrolyte is 1 to 80% by mass, the temperature of the electrolyte is 5 to 70 ° C., and the current density.
  • a preferred anodizing treatment is a method in which an aqueous solution of sulfuric acid, phosphoric acid or boric acid is used as the electrolytic solution and the treatment is performed with a direct current, but an alternating current can also be used.
  • the concentration of these acids is preferably 5 to 45% by mass, and the electrolytic treatment is preferably performed for 20 to 250 seconds at an electrolyte temperature of 20 to 50 ° C. and a current density of 0.5 to 20 A / cm 2 .
  • the thickness of the insulator layer As the thickness of the insulator layer, if the layer is thin, the effective voltage applied to the organic semiconductor increases, so the drive voltage and threshold voltage of the device itself can be lowered, but conversely between the source and gate. Therefore, it is necessary to select an appropriate film thickness, which is normally 10 nm to 5 ⁇ m, preferably 50 nm to 2 ⁇ m, and more preferably 100 nm to 1 ⁇ m.
  • any orientation treatment may be performed between the insulator layer and the organic semiconductor layer.
  • a preferable example thereof is a method for improving the crystallinity of the organic semiconductor layer by reducing the interaction between the insulator layer and the organic semiconductor layer by performing a water repellent treatment or the like on the surface of the insulator layer.
  • Silane coupling agents such as hexamethyldisilazane, octadecyltrichlorosilane, trichloromethylsilazane, and self-organized alignment film materials such as alkane phosphoric acid, alkane sulfonic acid, and alkane carboxylic acid are insulated in a liquid phase or gas phase state.
  • An example is a method in which the film is brought into contact with the surface of the film to form a self-assembled film, followed by appropriate drying treatment.
  • a method in which a film made of polyimide or the like is provided on the surface of the insulating film and the surface is rubbed so as to be used for liquid crystal alignment is also preferable.
  • the insulator layer can be formed by vacuum deposition, molecular beam epitaxy, ion cluster beam, low energy ion beam, ion plating, CVD, sputtering, JP-A-11-61406, 11-133205, JP-A 2000-121804, 2000-147209, 2000-185362, etc., dry process such as atmospheric pressure plasma method, spray coating method, spin coating method, blade coating Examples thereof include wet processes such as a method by coating such as a method, a dip coating method, a cast method, a roll coating method, a bar coating method, and a die coating method, and a patterning method such as printing and ink jetting.
  • the wet process is a method of applying and drying a liquid in which fine particles of inorganic oxide are dispersed in an arbitrary organic solvent or water using a dispersion aid such as a surfactant as required, or an oxide precursor, for example,
  • a so-called sol-gel method in which a solution of an alkoxide body is applied and dried is used.
  • the method for forming the organic thin film transistor of the present invention is not particularly limited, and may be a known method. According to a desired element configuration, the substrate is charged, the gate electrode is formed, the insulator layer is formed, the organic semiconductor layer is formed, and the source electrode is formed. It is preferable to form a series of device manufacturing steps up to the formation of the drain electrode without being exposed to the atmosphere at all, because the device performance can be prevented from being impaired by moisture, oxygen, etc. in the atmosphere due to contact with the atmosphere. When it is unavoidable that the atmosphere must be exposed to the atmosphere once, the process after the organic semiconductor layer is formed is not exposed to the atmosphere at all.
  • the surface of the insulating layer partially laminated with the source electrode and drain electrode is cleaned and activated by ultraviolet irradiation, ultraviolet / ozone irradiation, oxygen plasma, argon plasma, etc., and then the organic semiconductor layer is stacked.
  • ultraviolet irradiation ultraviolet / ozone irradiation
  • oxygen plasma argon plasma
  • the organic semiconductor layer is stacked.
  • some p-type TFT materials are exposed to the atmosphere once, and the performance is improved by adsorbing oxygen or the like. Therefore, depending on the material, the materials are appropriately exposed to the atmosphere.
  • a gas barrier layer may be formed on the whole or a part of the outer peripheral surface of the organic transistor element.
  • the gas barrier layer As a material for forming the gas barrier layer, those commonly used in this field can be used, and examples thereof include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl chloride, polyvinylidene chloride, and polychlorotrifluoroethylene. . Furthermore, the inorganic substance which has the insulation illustrated in the said insulator layer can also be used.
  • an organic thin film light emitting transistor that emits light using a current flowing between a source electrode and a drain electrode and controls light emission by applying a voltage to the gate electrode. That is, an organic thin film transistor can be used as a light emitting element (organic EL). Since the transistor for controlling light emission and the light emitting element can be integrated, the aperture ratio of the display can be improved and the cost can be reduced by the simplification of the manufacturing process, which provides a great practical advantage. When used as an organic light emitting transistor, it is necessary to inject holes from one of the source electrode and the drain electrode and electrons from the other, and the following conditions are preferably satisfied in order to improve the light emitting performance.
  • At least one of the source electrode and the drain electrode is a hole injecting electrode in order to improve the hole injecting property.
  • a hole injection electrode is an electrode containing a substance having a work function of 4.2 eV or higher.
  • the upper limit of the work function of the hole injection electrode is 7.0 eV, for example.
  • at least one of the source electrode and the drain electrode is preferably an electron injectable electrode.
  • An electron injecting electrode is an electrode containing a substance having a work function of 4.3 eV or less.
  • the lower limit of the work function of the electron injection electrode is, for example, 1.8 eV. More preferably, it is an organic thin film light emitting transistor provided with an electrode in which one is hole injecting and the other is electron injecting.
  • the hole injection layer In order to improve the hole injection property, it is preferable to insert a hole injection layer between at least one of the source electrode and the drain electrode and the organic semiconductor layer.
  • the hole injection layer include amine-based materials used as a hole injection material and a hole transport material in an organic EL device.
  • an electron injecting layer between at least one of the source electrode and the drain electrode and the organic semiconductor layer.
  • the electron injection material used for the organic EL element can be used for the electron injection layer as well as the hole. More preferably, one of the electrodes is provided with a hole injection layer and the other electrode is provided with an electron injection layer. It is a thin film light emitting transistor. [Example]
  • Synthesis Example 1 (Synthesis of Compound (46))
  • Compound (46) was synthesized as follows. The synthesis route is shown below. In a 300 ml three-necked flask, 3.00 g (8.87 mmol) of 4-bromo-p-terphenyl, 0.513 g (0.443 mmol) of tetrakistriphenylphosphine palladium, 0.169 g of copper (I) iodide (0 886 mmol) and replaced with argon.
  • Example 1 (Production of organic thin film transistor)
  • the organic thin film transistor shown in FIG. 7 was produced by the following procedure. First, the glass substrate 10 was ultrasonically cleaned with a neutral detergent, pure water, acetone, and ethanol for 30 minutes each, and then a gold (Au) film having a thickness of 40 nm was formed by a sputtering method to produce a gate electrode 15. Next, this substrate 10 was set in a film forming section of a thermal CVD apparatus.
  • polyparaxylene derivative [polyparaxylene chloride (Parylene)] (trade name; diX-C, manufactured by Daisan Kasei Co., Ltd.), which is a raw material for the insulating layer, was placed in a petri dish.
  • the thermal CVD apparatus is evacuated with a vacuum pump and depressurized to 5 Pa. Then, the evaporation part is heated to 180 ° C. and the polymerization part is heated to 680 ° C. and left for 2 hours. Formed.
  • the substrate was placed in a vacuum vapor deposition apparatus (ULVAC, EX-400), and the compound (46) was formed on the insulator layer as an organic semiconductor layer 13 having a thickness of 50 nm at a deposition rate of 0.05 nm / s. Filmed.
  • gold was deposited to a thickness of 50 nm through a metal mask, so that the source electrode 11 and the drain electrode 12 that were not in contact with each other were formed with a spacing (channel length L) of 75 ⁇ m.
  • an organic thin film transistor 3 was manufactured by forming a film so that the width (channel width W) of the source electrode and the drain electrode was 5 mm.
  • a gate voltage of ⁇ 40 V was applied to the gate electrode of the obtained organic thin film transistor, and a current was applied by applying a voltage between the source and drain.
  • holes are induced in the channel region (between the source and drain) of the organic semiconductor layer and operate as a p-type transistor.
  • the on / off ratio of the current between the source and drain electrodes in the current saturation region was 3 ⁇ 10 5 .
  • the field effect mobility ⁇ of holes was calculated from the following formula (A) and found to be 6 ⁇ 10 ⁇ 2 cm 2 / Vs.
  • I D (W / 2L) ⁇ C ⁇ ⁇ (V G ⁇ V T ) 2 (A)
  • ID is a source-drain current
  • W is a channel width
  • L is a channel length
  • C is a capacitance per unit area of the gate insulator layer
  • V T is a gate threshold voltage
  • V G is a gate voltage.
  • Example 2 (Production of organic thin film transistor) An organic thin film transistor was produced in the same manner as in Example 1 except that the compound (28) was used instead of the compound (46) as the material of the organic semiconductor layer. The obtained organic thin film transistor was p-type driven at a gate voltage V G of ⁇ 40 V in the same manner as in Example 1. Table 1 shows the results of measuring the on / off ratio of the current between the source and drain electrodes and calculating the field effect mobility ⁇ of the holes.
  • Example 3 (Production of organic thin film transistor) An organic thin film transistor was produced in the same manner as in Example 1 except that the compound (61) was used instead of the compound (46) as the material of the organic semiconductor layer. The obtained organic thin film transistor was p-type driven at a gate voltage V G of ⁇ 40 V in the same manner as in Example 1. Table 1 shows the results of measuring the on / off ratio of the current between the source and drain electrodes and calculating the field effect mobility ⁇ of the holes.
  • Example 4 (Production of organic thin film transistor) An organic thin film transistor was produced in the same manner as in Example 1 except that the compound (62) was used instead of the compound (46) as the material of the organic semiconductor layer. The obtained organic thin film transistor was p-type driven at a gate voltage V G of ⁇ 40 V in the same manner as in Example 1. Table 1 shows the results of measuring the on / off ratio of the current between the source and drain electrodes and calculating the field effect mobility ⁇ of the holes.
  • Example 5 (Production of organic thin film transistor) An organic thin film transistor was produced in the same manner as in Example 1 except that the compound (86) was used instead of the compound (46) as the material of the organic semiconductor layer. The obtained organic thin film transistor was p-type driven at a gate voltage V G of ⁇ 40 V in the same manner as in Example 1. Table 1 shows the results of measuring the on / off ratio of the current between the source and drain electrodes and calculating the field effect mobility ⁇ of the holes.
  • Comparative Example 1 (Production of organic thin film transistor) An organic thin film transistor was produced in the same manner as in Example 1 except that paracenylphenyl (Comparative Compound 1, hereinafter referred to as 6Ph) was used as the material for the organic semiconductor layer instead of Compound (46). The obtained organic thin film transistor was p-type driven at a gate voltage V G of ⁇ 40 V in the same manner as in Example 1. Table 1 shows the results of measuring the on / off ratio of the current between the source and drain electrodes and calculating the field effect mobility ⁇ of the holes.
  • 6Ph paracenylphenyl
  • Table 1 shows the results of measuring the on / off ratio of the current between the source and drain electrodes and calculating the field effect mobility ⁇ of the holes.
  • Comparative Example 2 (Production of organic thin film transistor) An organic thin film transistor was produced in the same manner as in Example 1 except that bisanthracenylacetylene (represented by Comparative Compound 2, hereinafter referred to as BAA) was used as the material for the organic semiconductor layer instead of the compound (46). did.
  • BAA bisanthracenylacetylene
  • the obtained organic thin film transistor was p-type driven at a gate voltage V G of ⁇ 40 V in the same manner as in Example 1.
  • Table 1 shows the results of measuring the on / off ratio of the current between the source and drain electrodes and calculating the field effect mobility ⁇ of the holes.
  • Example 6 (Production of organic thin film light-emitting transistor) An organic thin film light emitting transistor was produced by the following procedure. First, the surface of a Si substrate (also used as a P-type specific resistance 1 ⁇ cm gate electrode) was oxidized by a thermal oxidation method to produce a 300 nm thermal oxide film on the substrate to form an insulator layer. Further, after the SiO 2 film formed on one side of the substrate is completely removed by dry etching, chromium is deposited to a thickness of 20 nm by sputtering, and further gold (Au) is sputtered by 100 nm by sputtering. A film was formed as a gate electrode.
  • This substrate was ultrasonically cleaned with a neutral detergent, pure water, acetone and ethanol for 30 minutes each. Next, it is installed in a vacuum deposition apparatus (ULVAC, EX-900), and the compound (46) is deposited on the insulator layer (SiO 2 ) at a deposition rate of 0.05 nm / s to a thickness of 100 nm. Deposited as a layer. Next, a source electrode and a drain electrode provided with a hole injecting electrode (Au) and an electron transporting electrode (Mg) were formed as shown in FIG.
  • a metal mask 21 having a channel length of 75 ⁇ m and a channel width of 5 mm is installed in the same manner as described above, and the substrate 20 on which the organic semiconductor light emitting layer is formed is passed through the mask in a state where it is inclined 45 degrees with respect to the evaporation source.
  • Gold 22 was deposited to a thickness of 50 nm (FIGS. 8 (1) and (2)).
  • Mg23 was deposited to a thickness of 100 nm with the substrate 20 tilted 45 degrees in the reverse direction (FIG. 8 (3)).
  • FIG. 8 ( 4)
  • a source electrode and a drain electrode provided with a hole injecting electrode 22 (Au) and an electron transporting electrode 23 (Mg) were formed without being in contact with each other was fabricated.
  • -100 V was applied between the source and drain and -100 V was applied to the gate electrode, blue light emission of 40 cd / m 2 was obtained.
  • FIG. 9 shows an emission spectrum.
  • the organic thin film transistor of the present invention has a high response speed (driving speed) and is turned on / off by using a compound having a specific structure having high electron mobility as a material of the organic semiconductor layer.
  • the ratio is large and the performance as a transistor is high, and it can be used as an organic thin film light emitting transistor capable of emitting light.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Thin Film Transistor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention porte sur un transistor organique en couches minces, qui est doté d'au moins trois bornes d'une électrode grille, d'une électrode source et d'une électrode drain, d'une couche isolante et d'une couche de semi-conducteur organique, sur un substrat et qui régule un courant électrique entre les électrodes source-drain par application d'une tension à l'électrode grille. La couche de semi-conducteur organique comprend un composé organique spécifique comportant un groupe hydrocarboné aromatique ou un groupe cyclique hétéroaromatique et une structure d'acétylène au centre. Le transistor organique en couches minces émet de la lumière en faisant usage d'un courant électrique circulant entre les électrodes source-drain et régule la lumière d'émission par application d'une tension à l'électrode grille. De plus, l'invention porte sur un composé chimique approprié pour le transistor organique en couches minces.
PCT/JP2009/056933 2008-04-10 2009-04-03 Composé chimique utilisé pour un transistor organique en couches minces et transistor organique en couches minces WO2009125721A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2010507225A JP5452476B2 (ja) 2008-04-10 2009-04-03 有機薄膜トランジスタ用化合物及び有機薄膜トランジスタ

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008-102493 2008-04-10
JP2008102493 2008-04-10

Publications (1)

Publication Number Publication Date
WO2009125721A1 true WO2009125721A1 (fr) 2009-10-15

Family

ID=41161854

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/056933 WO2009125721A1 (fr) 2008-04-10 2009-04-03 Composé chimique utilisé pour un transistor organique en couches minces et transistor organique en couches minces

Country Status (3)

Country Link
JP (1) JP5452476B2 (fr)
TW (1) TW201000430A (fr)
WO (1) WO2009125721A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012091233A1 (fr) * 2010-12-31 2012-07-05 경상대산학협력단 Nouveau composé organique semi-conducteur et transistor organique à couches minces l'utilisant comme couche d'excitation
DE102012003876A1 (de) 2011-03-24 2012-09-27 Merck Patent Gmbh Verbindung mit einer C-C-Dreifachbindung
JP2013033823A (ja) * 2011-08-01 2013-02-14 National Institute Of Advanced Industrial & Technology 有機半導体材料
WO2014038708A1 (fr) 2012-09-10 2014-03-13 Dic株式会社 Dérivé du benzothiénobenzothiophène, matériau semi-conducteur organique et transistor organique
CN104662124A (zh) * 2012-09-21 2015-05-27 默克专利股份有限公司 具有c-c三键的化合物及其在液晶混合物中的用途
JP6355288B1 (ja) * 2017-04-26 2018-07-11 国立大学法人九州大学 電極、構造体およびその製造方法、接続構造体、並びに、その電極を用いた素子
WO2018199258A1 (fr) * 2017-04-26 2018-11-01 国立大学法人九州大学 Électrode, structure et procédé de fabrication associé, structure de connexion, et élément dans lequel ladite électrode est utilisée

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI515936B (zh) 2011-12-15 2016-01-01 友達光電股份有限公司 發光裝置及其製作方法

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05255151A (ja) * 1991-11-20 1993-10-05 Asahi Glass Co Ltd テトラフルオロベンゼン誘導体化合物及び液晶組成物
JPH0640970A (ja) * 1991-10-02 1994-02-15 Seiko Epson Corp トラン誘導体及びそれを含有する液晶組成物及びそれを用いた液晶表示素子
JPH10289786A (ja) * 1997-04-14 1998-10-27 Toyo Ink Mfg Co Ltd 有機エレクトロルミネッセンス素子材料およびそれを使用した有機エレクトロルミネッセンス素子
JP2004224710A (ja) * 2003-01-21 2004-08-12 Mitsui Chemicals Inc 光記録媒体およびアリールアセチレン化合物
WO2006059486A1 (fr) * 2004-12-02 2006-06-08 Konica Minolta Holdings, Inc. Materiau pour transistor a film mince organique, transistor a film mince organique, transistor a effet de champ, dispositif de commutation, materiau semi-conducteur organique et film semi-conducteur organique
JP2006518545A (ja) * 2003-02-19 2006-08-10 エルジー エレクトロニクス インコーポレーテッド 有機電界発光素子
US20060234084A1 (en) * 2005-04-19 2006-10-19 Eastman Kodak Company OLED device with improved luminescent layer
JP2007169620A (ja) * 2005-11-25 2007-07-05 National Institute Of Advanced Industrial & Technology 共役系透明高分子材料
WO2007105473A1 (fr) * 2006-03-10 2007-09-20 Konica Minolta Holdings, Inc. Materiau semiconducteur organique, film semiconducteur organique, dispositif semiconducteur organique, et transistor a film mince organique
WO2007123030A1 (fr) * 2006-04-19 2007-11-01 Konica Minolta Holdings, Inc. Matériau semi-conducteur organique, couche semi-conductrice organique, dispositif semi-conducteur organique, et transistor à couche mince organique
JP2007311609A (ja) * 2006-05-19 2007-11-29 Konica Minolta Holdings Inc 有機半導体材料、有機半導体膜、有機半導体デバイス及び有機薄膜トランジスタ
WO2007145293A1 (fr) * 2006-06-16 2007-12-21 Asahi Glass Company, Limited Nouveaux composés aromatiques contenant du fluor, matériaux semi-conducteurs organiques et dispositifs à films minces organiques
JP2008004725A (ja) * 2006-06-22 2008-01-10 Konica Minolta Holdings Inc 有機半導体材料、有機半導体膜、有機半導体デバイス及び有機薄膜トランジスタ
JP2008078279A (ja) * 2006-09-20 2008-04-03 Konica Minolta Holdings Inc 有機半導体材料、有機半導体膜、有機半導体デバイス及び有機薄膜トランジスタ
WO2008044695A1 (fr) * 2006-10-12 2008-04-17 Idemitsu Kosan Co., Ltd. Dispositif de transistor organique à couche mince et transistor organique à couche mince émetteur de lumière
JP2008103464A (ja) * 2006-10-18 2008-05-01 Konica Minolta Holdings Inc 有機半導体材料、有機半導体膜、有機半導体デバイス及び有機薄膜トランジスタ
JP2008251575A (ja) * 2007-03-29 2008-10-16 Konica Minolta Holdings Inc 有機薄膜トランジスタの形成方法、及び有機薄膜トランジスタ

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0640970A (ja) * 1991-10-02 1994-02-15 Seiko Epson Corp トラン誘導体及びそれを含有する液晶組成物及びそれを用いた液晶表示素子
JPH05255151A (ja) * 1991-11-20 1993-10-05 Asahi Glass Co Ltd テトラフルオロベンゼン誘導体化合物及び液晶組成物
JPH10289786A (ja) * 1997-04-14 1998-10-27 Toyo Ink Mfg Co Ltd 有機エレクトロルミネッセンス素子材料およびそれを使用した有機エレクトロルミネッセンス素子
JP2004224710A (ja) * 2003-01-21 2004-08-12 Mitsui Chemicals Inc 光記録媒体およびアリールアセチレン化合物
JP2006518545A (ja) * 2003-02-19 2006-08-10 エルジー エレクトロニクス インコーポレーテッド 有機電界発光素子
WO2006059486A1 (fr) * 2004-12-02 2006-06-08 Konica Minolta Holdings, Inc. Materiau pour transistor a film mince organique, transistor a film mince organique, transistor a effet de champ, dispositif de commutation, materiau semi-conducteur organique et film semi-conducteur organique
US20060234084A1 (en) * 2005-04-19 2006-10-19 Eastman Kodak Company OLED device with improved luminescent layer
JP2007169620A (ja) * 2005-11-25 2007-07-05 National Institute Of Advanced Industrial & Technology 共役系透明高分子材料
WO2007105473A1 (fr) * 2006-03-10 2007-09-20 Konica Minolta Holdings, Inc. Materiau semiconducteur organique, film semiconducteur organique, dispositif semiconducteur organique, et transistor a film mince organique
WO2007123030A1 (fr) * 2006-04-19 2007-11-01 Konica Minolta Holdings, Inc. Matériau semi-conducteur organique, couche semi-conductrice organique, dispositif semi-conducteur organique, et transistor à couche mince organique
JP2007311609A (ja) * 2006-05-19 2007-11-29 Konica Minolta Holdings Inc 有機半導体材料、有機半導体膜、有機半導体デバイス及び有機薄膜トランジスタ
WO2007145293A1 (fr) * 2006-06-16 2007-12-21 Asahi Glass Company, Limited Nouveaux composés aromatiques contenant du fluor, matériaux semi-conducteurs organiques et dispositifs à films minces organiques
JP2008004725A (ja) * 2006-06-22 2008-01-10 Konica Minolta Holdings Inc 有機半導体材料、有機半導体膜、有機半導体デバイス及び有機薄膜トランジスタ
JP2008078279A (ja) * 2006-09-20 2008-04-03 Konica Minolta Holdings Inc 有機半導体材料、有機半導体膜、有機半導体デバイス及び有機薄膜トランジスタ
WO2008044695A1 (fr) * 2006-10-12 2008-04-17 Idemitsu Kosan Co., Ltd. Dispositif de transistor organique à couche mince et transistor organique à couche mince émetteur de lumière
JP2008103464A (ja) * 2006-10-18 2008-05-01 Konica Minolta Holdings Inc 有機半導体材料、有機半導体膜、有機半導体デバイス及び有機薄膜トランジスタ
JP2008251575A (ja) * 2007-03-29 2008-10-16 Konica Minolta Holdings Inc 有機薄膜トランジスタの形成方法、及び有機薄膜トランジスタ

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Meruku Shiyaku Catalog 2002-2003", MERUKU KABUSHIKI KAISHA, 1 April 2002 (2002-04-01), pages 676 *
ROY ET AL.: "Functionalized Arylacetylene Oligomers for Organic Thin-Film Transistors(OTFTs)", ADV. MATER., vol. 17, no. 10, 2005, pages 1258 - 1261 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012091233A1 (fr) * 2010-12-31 2012-07-05 경상대산학협력단 Nouveau composé organique semi-conducteur et transistor organique à couches minces l'utilisant comme couche d'excitation
DE102012003876A1 (de) 2011-03-24 2012-09-27 Merck Patent Gmbh Verbindung mit einer C-C-Dreifachbindung
WO2012126564A1 (fr) 2011-03-24 2012-09-27 Merck Patent Gmbh Composés à triple liaison c-c
US9777217B2 (en) 2011-03-24 2017-10-03 Merck Patent Gmbh Compounds having a C—C triple bond
JP2013033823A (ja) * 2011-08-01 2013-02-14 National Institute Of Advanced Industrial & Technology 有機半導体材料
US9490433B2 (en) 2012-09-10 2016-11-08 Dic Corporation Benzothienobenzothiophene derivative, organic semiconductor material, and organic transistor
WO2014038708A1 (fr) 2012-09-10 2014-03-13 Dic株式会社 Dérivé du benzothiénobenzothiophène, matériau semi-conducteur organique et transistor organique
CN104662124A (zh) * 2012-09-21 2015-05-27 默克专利股份有限公司 具有c-c三键的化合物及其在液晶混合物中的用途
CN104662124B (zh) * 2012-09-21 2017-06-16 默克专利股份有限公司 具有c‑c三键的化合物及其在液晶混合物中的用途
TWI607983B (zh) * 2012-09-21 2017-12-11 馬克專利公司 含有ｃ－ｃ參鍵的化合物及其在液晶混合物中的用途
US9868905B2 (en) 2012-09-21 2018-01-16 Merck Patent Gmbh Compounds having a C—C triple bond and use thereof in liquid-crystal mixtures
JP6355288B1 (ja) * 2017-04-26 2018-07-11 国立大学法人九州大学 電極、構造体およびその製造方法、接続構造体、並びに、その電極を用いた素子
WO2018199258A1 (fr) * 2017-04-26 2018-11-01 国立大学法人九州大学 Électrode, structure et procédé de fabrication associé, structure de connexion, et élément dans lequel ladite électrode est utilisée
JP2018186261A (ja) * 2017-04-26 2018-11-22 国立大学法人九州大学 電極、構造体およびその製造方法、接続構造体、並びに、その電極を用いた素子

Also Published As

Publication number Publication date
JPWO2009125721A1 (ja) 2011-08-04
JP5452476B2 (ja) 2014-03-26
TW201000430A (en) 2010-01-01

Similar Documents

Publication Publication Date Title
JP5368797B2 (ja) 有機薄膜トランジスタ素子及び有機薄膜発光トランジスタ
JP5490005B2 (ja) 有機薄膜トランジスタ用化合物及びそれを用いた有機薄膜トランジスタ
JP5337490B2 (ja) 有機薄膜トランジスタ及び有機薄膜発光トランジスタ
JP5666474B2 (ja) 多環縮環化合物、及び、それを用いた有機薄膜トランジスタ
WO2010016511A1 (fr) Composé pour transistor à film mince organique et transistor à film mince organique l'utilisant
JP5460599B2 (ja) 有機薄膜トランジスタ用化合物及びそれを用いた有機薄膜トランジスタ
WO2010024388A1 (fr) Composé pour transistor à couches minces organiques et transistor à couches minces organique utilisant ce composé
JP5299807B2 (ja) ベンゾジチオフェン誘導体並びにそれを用いた有機薄膜トランジスタ及び有機薄膜発光トランジスタ
JPWO2007094361A1 (ja) 有機薄膜トランジスタ及び有機薄膜発光トランジスタ
WO2011074231A1 (fr) Composé polycyclique à cycles fusionnés et transistor organique en couches minces le contenant
JPWO2008059817A1 (ja) 有機薄膜トランジスタ及び有機薄膜発光トランジスタ
JP5452476B2 (ja) 有機薄膜トランジスタ用化合物及び有機薄膜トランジスタ
JPWO2008069061A1 (ja) 有機薄膜トランジスタ及び有機薄膜発光トランジスタ
JPWO2008062841A1 (ja) 有機薄膜トランジスタ及び有機薄膜発光トランジスタ
JP2015109455A (ja) 有機薄膜トランジスタ
JP5308164B2 (ja) 有機薄膜トランジスタ及び有機薄膜発光トランジスタ
JP5528330B2 (ja) 有機薄膜トランジスタ用化合物及びそれを用いた有機薄膜トランジスタ
JP5452475B2 (ja) 有機薄膜トランジスタ用化合物及びそれを用いた有機薄膜トランジスタ
JP5329404B2 (ja) 有機薄膜トランジスタ及び有機薄膜発光トランジスタ
JP2008147587A (ja) 有機薄膜トランジスタ及び有機薄膜発光トランジスタ
JP2010275239A (ja) 新規な縮合芳香環化合物及びそれを用いた有機薄膜トランジスタ
JP5308162B2 (ja) 有機薄膜トランジスタ及び有機薄膜発光トランジスタ

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09731002

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2010507225

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09731002

Country of ref document: EP

Kind code of ref document: A1